Motor fuel



MOTOR FUEL Milton Kosmin, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application December 29, 1953 Serial No. 401,093

20 Claims. (Cl. 52-.5)

The present invention relates to a special fuel suitable for use in jet and reciprocating engines, particularly as employed in various types of aircraft.

An object of the invention is to provide a supplementary emulsion fuel for jet and reciprocating engines to provide the increased power necessary for aircraft takeolfs and emergency combat operations. It is also an object of the present invention to provide an emulsion fuel which will provide water to cool the interior of combustion zones of engines operating under high temperature conditions. It is a further object to provide emulsions which may be prepared with water, such as may be found in various localities with varying amounts and types of impurities.

The use of water injection in the operation of jet and reciprocating engines for emergency combat operations and increased power required in take-offs provides inatent" fated condensation product of tridecanol or other x0 alcohols as described herein with from 1 to 10 moles of ethylene oxide; (b) alkaline salts of dihexyl sulfophthalate; and (c) condensation products of tridecanol or other Oxo alcohols as described herein; and mixtures of two or three of the above groups of (a), (b) and (c).

The hydrocarbon fuel employed as one of the constituents of the emulsions defined in the present invention may be a paralfinic or naphthenic type boiling in the motor fuel boiling range, and generally characterized by an extremely low pour point. A typical hydrocarbon fuel of this type for jet engines is a low vapor pressure liquid made from a mixture of gasoline and cracked kerosene. For reciprocating engines, the conventional aircraft type gasoline may be employed.

The water employed in the preparation of the present fuel combinations need notbe distilled nor specifically purified but may contain naturally occurring amounts of soluble salts such as carbonates, chlorides and sulfates of calcium,magnesium and sodium,-such as are commonly found in hard water regions.

creased thrust due to both the increased volume and velocity of the gases discharged from the engine.

It has now been found that the use of water in emulsion form is especially advantageous for the present pur pose. It has also been found that a specific combination of emulsifiers makes it possible to provide an emergency fuel from (i) a hydrocarbon fuel boiling in the motor fuel boiling range ordinarily employed for jet and reciproeating engines, together with (2) 'water such as may be naturally available containing various imp urities occurring in such natural water.

The use of the above-described emulsion of a hydrocarbon fuel boiling in the motor fuel boiling range together with water for directinjectiondn jet or reciproeating enginesresults in a reduction ofthe temperature of the fuel-air charge and also by direct cooling of the combustion zone. In case of thereciprocating engines such direct cooling occurs in the cylinder, making it possibleto obtain a greater power output from the engine. It is also found that reduction of carbon deposition occurs in the use of water as above described. i The present emulsions may also be employed in order to further after-burning in the operation of jet engines. Thus, the engine may be operated in accordance with the method wherein fuel is separately introduced into the gas stream after the primary combustion zone in order to complete the combustion and to create a large amount of exit gas from the jet engine. In this way, the thrust obtained may also be increased, for example, in take-offs and under combat conditions in which additional power is required. The present emulsion has the advantage that such supplementary fuel may be provided directly from the conventional hydrocarbon fuel and water so that only the emulsifyingagent need bepro- The emulsifying 1 agent employed in the present emulsion fuels may be a single emulsifying component or a combination thereof. The emulsifiers employed in the present invention are (1) an alkaline salt of clihexyl sulfophthalate, such as an amine salt or butylarnmonium dihexylssulfophthalate; and/or 2) an alkaline salt of the sulfated condensation product of alcohols condensed with ethylene oxide. The alkaline salt of the sulfated condensation product is based upon the ethylene oxide addition product with a highly branched monohydric primary alcohol having the molecular configuration of an alcohol produced by the Oxo process from an olefin such as triisobutylene and tetrapropylene with from 1 to 10, preferably to 5 moles of ethylene oxide per mole of alcohol. A preferred embodiment in the present invention is the use of a mixture of isomeric monohydric primary tridecyl alcohols, said alcohols being derived from the catalyzed 0x0 reaction of carbon monoxide and hydrogen with a material of a classlconsisting of polyisobutylenes and polypropylenes. The third componet is (3) an ethylene oxide condensation product of tridecanol with 1-10 moles of ethylene oxide.

When polymer olefins such as polyisobutylene or polypropylene are reacted according to the 0x0 reaction with carbon monoxide and hydrogen in the presence of the catalyst containing cobalt carbonyl, thorium and mag nesium oxides or allied catalytic materials, a mixture of isomeric alcohols having a wide boiling range is obtained. The alcohols may be manufactured by the process described in the United States Bureau of Mines Report of vided as aminor constituent together with commonly available fuel. g p i The method for employing the present emulsion fuel in order to suppress carbon formation and to cool the interior combustion zones of jet and reciprocating engines during operation thereof comprises the introduction of waterto provide the supplementary emulsion Investigation No. 4-270, dated June 1948. In view of the presence of a number of isomers of triisobutylene or tetrapropylene, for example, in the polymer olefins which are treated according to the 0x0 reaction and furthermore since there is considerable isomerization, polymerization and depolymerization of the olefins due to the catalytic action, the resulting alcoholic product contains a large number of different alcohols, some of which are polyhydric alcohols. By reason of the large number of compounds present in the 0x0 reaction product it has so far been impossible to ascertain the exact composition of this product.

The formation of the present condensation products is carried out by passing ethylene oxide either'as, a gas or as a liquid into the 0x0 alcohol, such as tridecyl al- Tilridecanolil mole ethyl tie-oxide condensation cohol i the presence of van alkaline catalyst ..such as caustic soda or potash. Using from 0.25% to 1.5% by weight of the catalyst based on the alcohol is satisfactory. The condensates vare ..thjen sulfatcd ;by conventional methods, which the sulfated product is neutralized to form the alkaline salt, such ,as :the sodium, potassium, ammonium or an ,alkyl amine salt. The amine salt may e prepared by .stheuseof mono, -dior trimethylamines or the .corresponding'ethyl or ethanolamines.

in preparing :the mixture of the :said emulsifying :agents ot the two typesdescribed above, ,itihas been :found that the proportion @thereof may varyfrom 01311 to 4: 1 :parts by weight ofithe said phthalatetoithe said condensation product, a preferred ratio being equal proportions by weight. in the preparation ofthe emulsion .fuels of the present invention it has been found that emulsions may desirably he prepared .in :-the :proportion of 88 parts :by weight of water with :12 :parts of the hydrocarbon and emulsifier. However, @the present emulsions may contain from 22% to 94.7% water; 5 to 60% of the hydrocarbon -and-0.i% to 6% of the emulsifier.

The examples below illustrate some of the spe'cifi embodiments ,of -:the :present-invention.

Examp -1 An emulsion was preparedby mixing the following:

o 7 Percent Hydro ar on fuel V Y.-. H -"c", 11.4 Butylamine salt of dihexyl sulfQPhthalate 0.3

Sodium sa t o lis ed t idecan l-i mole eth lene. oxide oondensation product (alcohol derived 1b 0X0 process) product (alcohol derived by Dxo rprocess) ..-,.'-1-. .0.15 Wa er (-30.0 sp; in. in. hardness) Va. -..a-.:. 88.0

fifhe aboye combination was tested to determine ;-the stability of the-emulsion as formulated above and also with each of thesuriace-active agents prescntalone with the oil and-Water. The emulsion stability data for the above examples are set forth ..below:

"The ineasure of "emulsion stability as employedlin' the p e test i t e mount of l quid separated afte '29 hours or standing at 30 it usf m the b vcircsutts' ha 'lthe' 'cinhinaa tion ofthe surface active agents in'fthe ernulsion'fuel results in a product having greater stability than can he obtained from a .Single surface-active agent employed alone. When the ethylene oxide condensation product with tridecanol or other 1030' alcohols) is employed with the sodium salt 'olf a suljfate'd'condensationproduct of this ,type it',-is preferred torha've the formerrpresent in equal proportion ,toone-half as muchas the sodium salt of the sulfate d derivative. .A typical mixture is shown in'EXan ple l.

ltQhas beeniound .that'the above specific emulsifying agents vemployed singly, as .a binary system or as a ternary system, results .in the formation of hydrocarbon- Water emulsions of the greatest utility in vieWof-{the remarkablejtolerance which the ,said emulsions display towards water, hardness and the presence of: soluble s alts FiQ asarelifoundin naturally occurring Waters, in various 4 regions. However, the present ..inyention also contemlates the of single emulsifiers. Examples of such emulsifiers are the alkaline salts of dihexyl sulfophthalate such as amine salts, and the alkaline salts of the sulfated condensation product of tridecanol and similar 0x0 alcohols with ethylene oxide. Typical alkaline salts are the sodium, ammoniurnand amine salts, such as methyl, ethyl, prcpyl, butyl, pentyl and hexyl amine salts em ployed as the mono, 'di-, 'or triamines ,or thecorresponding alkanolarnines. Another class of emulsifiers rare the ethylene oxide condensation products of tridecanoland other OX0 alcohols as described above. .Suchlatter condcnsation' products .prcier ably have jrom 1 to '10 moles of ethylene oxide per mole of the alcohol.

The emulsion-stability values- 0f other fuels based upon various emulsifiers are set forth below:

Percent Li uid "Water Separated lrom Emuhmc s 11.0 Hard- =,E mu sion ness Um '5 Min. 'ZQHrs.

Dirneth 1 Amino salt of di-hcxyl-A A s'uliop ithalate 1:2 '50 8 Isopropyl Amine salt oidi-hexyl-i-e 0.6 5 -60:' *0

sulfop...,thalate ...,..r 1.2 I 50 .0 'Butylaminc salt of di-hexyl-4-sul- 1:23 50 '0 Na salt of enlisted tridecauol+ 5 1.2 j-liO 0 1 E. 0% egg. Dimebhyla m na 'ssalt of snlfated E fi i ecanol E. O,. .1- 2 5. .2 Isopiopylamine salt of sulfat I i idc anclhi-E- .Q- 3- 2 50 .20.. n-Butylainine salt t 7 hshalat 3). 9 ,50 0;

" Contains 25%of condensation productof 1 moleethylene-oxide'per' mole trldecanol.

What is claimed -is:- I

A impr motor fue whi hccmpri s o ,.5.% tfl 60;% of hydrocarbons bpilingin themotorfuel boiling r n e. nl fied w t wt to ;8'% of at a the li iie scnha e i -Ithe pr senc of the combin ion-9M4) -:t 1 %@o an e al ncsal cftd the vk ulfqphtha at togethe wit ,(b) --1.0-, t -fit c van sulfated condensation. 'pliqduct of eth m tu .Q hi h y-branched. nonchv he mo a t cnfigu e iqn Q the 0X p c cs om ano cfim th .-cla .ccn i' s citi lv obfi ylc e n PQ YP QP1encS,-3 d (c) lib 6% o a ethy e e ox d o de s on p duc th an l oho desc bed whi as been qrzc n d Tin fro moles of ethylene oxide which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

4. An improved motor fuel which comprises hydrocarbons boiling in the motor fuel boiling range, emulsified with water in the presence of 0.1% to 6% of an alkaline salt of a sulfated condensation product of tridecanol with from 1 to 10 moles of ethylene oxide which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash per mole of the said tridecanol together with 0.1% to 6% of an alkaline base salt of dihexyl sulfophthalate.

5. An improved motor fuel which comprises hydrocarbons boiling in the motor fuel boiling range, emulsified with water as the disperse phase in the presence of the combination of 0.1% to 6% of an alkaline salt of dihexyl sulfophthalate together with 0.1% to 6% of an alkaline salt of a sulfated condensation product of ethylene oxide with a mixture of highly-branched monohydric primary alcohols having the molar configuration of an alcohol produced by the x0 process from an olefin of the class consisting of polyisobutylenes and polypropylenes which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

6. An improved motor fuel which comprises from to 60% of hydrocarbons boiling in the motor fuel boiling range, 22% to 94.7 of water; 0.1% to 6% of butylamine salt of hexyl-4-sulfophthalate and from 0.1% to 6% of the ethylene oxide condensation product of sulfated tridecanol which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

7. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 22% to 94.7% of water, and 0.1% to 6% of the sodium salt of the sulfated condensation product of tridecanol with from 1 to 10 moles of ethylene oxide which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

8. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 22% to 94.7% of water, and 0.1% to 6% of the butylamine salt of the sulfated condensation product of tridecanol with from 1 to 10 moles of ethylene oxide which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

9. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 34% to 94.7% of water, and 0.1% to 6% of an alkaline salt of dihexyl sulfophthalate.

10. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 34% to 94.7% of water, and 0.1% to 6% of an amine salt of dihexyl sulfophthalate.

11. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 34% to 94.7% of water, and 0.1% to 6% of the butylamine salt of dihexyl sulfophthalate.

12. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 28% to 94.7% of water, and 0.1% to 6% of alkaline salts of the sulfated condensation product of tridecanol with from 1 to 10 moles of ethylene oxide which has been condensed in the presence or" an alkaline catalyst selected from the group consisting of caustic soda and caustic potash, and alkaline salts of dihexyl sulfophthalate.

13. A method for suppressing carbon formation and cooling the interior combustion zones of jet and reciprocating engines during operation thereof, said operation including introducing oxygen-containing gas and by- 6 drocarbon fuel into a combustion zone, and adding thereto an aqueous emulsion comprising from 5% to of hydrocarbons boiling in the motor fuel boiling range, 28% to 94.7% of water, 0.1% to 6% of butylamine salt of dihexyl-4-sulfophthalate, and from 0.1% to 6% of the sodium salt of the ethylene oxide condensation product of sulfated tridecanol which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

14. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 22% to 94.7% of water, and 0.10% to 6% of an alkaline salt of the sulfated condensation product of tridecanol with from 1 to 10 moles of ethylene oxide, 0.1% to 6% of an alkaline salt of dihexyl sulfophthalate, and 0.1% to 6% of a condensation product of tridecanol with from 1 to 10 moles of ethylene oxide per mole of the said tridecanol which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

15. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 22% to 94.7% of water, and 0.1% to 6% of an alkaline salt of the sulfated condensation product of l to 10 moles of ethylene oxide with a. mixture of highlybranched monohydric primary alcohols having the molar configuration of an alcohol produced by the 0x0 process from an olefin of the class consisting of polyisobutylenes and polybutylenes, 0.1% to 6% of an alkaline salt of dihexyl sulfophthalate, and 0.1% to 6% of a condensation product of l to 10 moles of ethylene oxide per mole of said Oxo alcohols which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

16. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 28% to 97% of water, and 0.10% to 6% of an alkaline salt of the sulfated condensation product of tridecanol with from 1 to 10 moles of ethylene oxide, and 0.1% to 6% of a condensation product of tridecanol with from 1 to 10 moles of ethylene oxide which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

17. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, 34% to 94.7% of water, and 0.10% to 6% of a condensation product of tridecanol with from 1 to 10 moles of ethylene oxide which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

18. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the inotor fuel boiling range, 28% to 94.7% of Water, and 0.10% to 6% of an alkaline base salt of dihexyl sulfophthalate, and 0.10% to 6% of a condensation product of tridecanol with from 1 to 10 moles of ethylene oxide which has been condensed in the presence of an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

19. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel coiling range, emulsified with 22% to 94.8% of water in the presence of (a) 0.1% to 6% of an alkaline salt of a sulfated condensation product of an Oxo alcohol with from 1 to 10 moles of ethylene oxide per mole of the said alcohol, together with (b) 0.1% to 6% of an alkaline salt of dihexyl sulfophthalate, and (c) 0.1% to 6% of a condensation product of an OX0 alcohol with from 1 to 10 moles of ethylene oxide, the said condensation being conducted with an alkaline catalyst selected from the group consisting of caustic soda and caustic potash.

20. An improved motor fuel which comprises from 5% to 60% of hydrocarbons boiling in the motor fuel boiling range, emulsified with 22% to 94.8% of water in lh p wncc o (a) 0.11% to of an M al ne a t ilefmnaasfl iad iaih fi o th P v afiulfatfidlc n ii np du m i i wano w t -i on; BMW TF5 Pmwwg 1 to 10 moles ,oi ethylsne oxick per; mole of the -,ai d 'f M 1 v iridcgano l, tpgeihar with (b) 3.1% to 6% of an alkalipge 3 1 fi 9 4 1933 l; of dihqxyl uifo htm aa and (c) 0.1% m 5% pf a 5 2 14 aK k tn --V-- ii 193 gond ansation product of tridccanoi with 1 111 1 to 19 9 5 Rolls}! 5111? 9 moles of ethylene oxide the said ccndensation product bemg ostaln ed 1n ins presence of an mkahne catalysi sc- ORHU? PATEBT" I le ct ed f l'QlTl the .gmup consisting sf caustic soda and 213,628 G1'eat 3 1:it ain,, M21131, 1924 ,c aust ic potash. 10 879,689 finance H0136, 1942 

1. AN INPROVED MOTOR FUEL WHICH COMPRISES FROM 5% TO 60% OF HYDROCARBONS BOILING IN THE MOTOR FUEL BOILING RANGE, EMULSIFIED WITH 22% TO 94% OF WATER AS THE DISPERSE PHASE IN THE PRESENCE OF THE COMBINATIONS OF (A) 0.1% TO 6% OF AN ALKALINE SALT OF DIHEXYL SULFOPHTHALATE TOGETHER WITH (B) 0.1% TO 6% OF AN ALKALINE SALT OF A SULFATED CONDENSATION PRODUCT OF ETHYLENE OXIDE WITH A MIXTURE OF HIGHLY-BRANCHED MONOHYDRIC PRIMARY ALCOHOLS HAVING THE MOLAR CONFIGURATION OF AN ALCOHOL PRODUCED BY THE OXO PROCESS FROM AN OLEFIN OF THE CLASS CONSISTING OF POLYISOBUTYLENES AND POLYPROPYLENES, AND (C) 0.1% TO 6% OF AN ETHYLENE OXIDE CONDENSATION PRODUCT WITH AN ALCOHOL DESCRIBE IN (B) WHICH HAS BEEN CONDENSED IN THE PRESENCE OF AN ALKALINE CATALYST SELECTED FROM THE GROUP CONSISTING OF CAUSTIC SODA AND CAUSTIC POTASH. 